TW202118130A - Adjusting material for contact surface of solid electrolyte and composite electrolyte system thereof - Google Patents

Abstract

The invention provides an adjusting material for contact surface of solid electrolyte and composite electrolyte system thereof. The adjusting material for contact surface of solid electrolyte is mainly composed of a polymer substrate capable of transmitting metallic ions inside the material, a dissociable metallic salt and an additive material as a plasticizer. The adjusting material is applied to a surface of a solid electrolyte to construct a face-to-face transmission mode. Therefore, the problems of the high resistances caused by the directly contact of the solid electrolyte are eliminated.

Description

Solid electrolyte junction adjusting material and its mixed electrolyte system

The present invention relates to an electrolyte in an electrochemical system, in particular to a solid electrolyte junction adjustment material and a hybrid electrolyte system containing the solid electrolyte junction adjustment material.

In today’s era of energy crisis and energy revolution, secondary chemical energy plays a very important role, especially metal ion batteries with high specific energy and specific power advantages, such as sodium ion batteries, aluminum ion batteries, Magnesium-ion batteries, or lithium-ion batteries, are used in information and consumer electronics products. Recently, they have expanded to the category of energy and transportation.

Common electrolyte systems in secondary chemical energy can be mainly divided into liquid electrolyte systems and solid electrolyte systems. The above solid electrolyte systems also cover inorganic electrolytes and organic polymer electrolytes. In order to adapt the liquid electrolyte system to battery systems with working voltages up to 3-4V, such as lithium-ion batteries, water is eliminated as the solvent, but organic solvents and electrolyte salts that are not easily decomposed under high voltage are used as the main components. However, these organic solvents are flammable, volatile, and cause battery leakage and cause explosions and fires. Based on safety considerations, electrolyte systems have shifted from liquid to higher-safety solid electrolyte systems, especially inorganic solid electrolyte systems with high thermal stability, such as oxide solid electrolytes. But oxide solid electrolyte cannot The characteristics of deformation cause some application problems. For example, the interface between oxide solid electrolytes or between oxide solid electrolytes and the active material of the electrode layer is mainly only point-to-point contact. The liquid electrolyte or colloidal electrolyte is in contact with another material through a surface-to-surface method or a similarly wettable coating type. Therefore, high interfacial impedance has become one of the important bottlenecks in the application of oxide solid electrolytes in secondary chemical energy. .

In view of this, the present invention proposes a new solid electrolyte junction adjustment material and its hybrid electrolyte system to solve the above-mentioned problems.

The main purpose of the present invention is to provide a solid electrolyte junction adjustment material and a hybrid electrolyte system thereof to solve the problem of high interface impedance of the inorganic solid electrolyte.

The present invention provides a solid electrolyte junction adjustment material, which is used in a metal electrochemical system. The solid electrolyte junction adjustment material consists of a polymer substrate that can allow metal ions to move inside the material and a dissociable metal salt. As a plasticizer additive material mixed together.

The present invention further provides a hybrid electrolyte system containing the above-mentioned solid electrolyte junction adjustment material, which comprises a first particle, which is a first inorganic solid electrolyte; and a second particle, which is selected from the group consisting of the second inorganic solid electrolyte and the blunt Ceramic material or active material; and a bridge portion located between the first particle and the second particle, the bridge portion is formed by the above-mentioned solid electrolyte junction adjustment material, and the solid electrolyte junction adjustment The material then forms an ion transport path between the first particle and the second particle.

The present invention further provides a hybrid electrolyte system containing the above solid electrolyte junction adjustment material, which includes a first particle, which is a first inorganic solid electrolyte; a second Particles, which are selected from a second inorganic solid electrolyte, a passive ceramic material or an active material; and a first shell layer, which covers the outer surface of the first particle; wherein the first shell layer is made of the above-mentioned solid electrolyte The junction adjustment material is formed, and the solid electrolyte junction adjustment material then forms an ion transfer path for the first particles and the second particles.

Detailed descriptions are given below by specific embodiments, so that it will be easier to understand the purpose, technical content, features, and effects of the present invention.

1, 2, 3‧‧‧Hybrid electrolyte system

11‧‧‧First particle

12‧‧‧Second particle

13‧‧‧Bridge

14‧‧‧First adulterant

15‧‧‧Second adulterant

16‧‧‧Artificial Passive Film

21‧‧‧First Shell

22‧‧‧Second Shell

Figure 1a is a schematic diagram of a hybrid electrolyte system constructed using the solid electrolyte junction adjustment material of the present invention.

Figure 1b is a schematic view of the contact surface between the bridge portion of the present invention and the inorganic solid electrolyte.

Fig. 1c-Fig. 1g are schematic diagrams of different embodiments of the hybrid electrolyte system of the present invention.

Figures 2a-2h are schematic diagrams of different embodiments of the hybrid electrolyte system of the present invention.

Fig. 2a' is a partial enlarged view of Fig. 2a.

Figures 3a to 3f are schematic diagrams of different embodiments of the hybrid electrolyte system of the present invention.

Figure 4 is a schematic diagram of the relationship between ion conductivity and frequency of different materials.

In order to make the advantages, spirit and features of the present invention easier and clearer to understand, the following embodiments will be used for detailed and discussion with reference to the drawings. It should be stated that these embodiments are only representative embodiments of the present invention, and are not intended to limit the implementation modes and scope of the present invention to only these embodiments. The purpose of providing these embodiments is only to make the disclosure of the present invention The content is more thorough and easy to understand.

The terms used in the various embodiments disclosed in the present invention are only used for the purpose of describing specific embodiments, and are not intended to limit the various embodiments disclosed in the present invention. Unless otherwise clearly indicated, the singular form used also includes the plural form. Unless otherwise defined, all terms (including technical and scientific terms) used in this specification have the same meaning as commonly understood by those of ordinary skill in the art to which the various embodiments disclosed in the present invention belong. The above-mentioned terms (such as those defined in general use dictionaries) will be interpreted as having the same meaning as the contextual meaning in the same technical field, and will not be interpreted as having idealized or overly formal meanings, unless It is clearly defined in the various embodiments disclosed in the present invention.

In the description of this specification, description with reference to the terms "an embodiment", "a specific embodiment", etc. means that the specific feature, structure, material or characteristic described in conjunction with the embodiment is included in at least one embodiment of the present invention . In this specification, the schematic representations of the above-mentioned terms do not necessarily refer to the same embodiment. Moreover, the described specific features, structures, materials or characteristics can be combined in any one or more embodiments in a suitable manner.

In the description of the present invention, unless otherwise specified or limited, it should be noted that the terms "coupled", "connected", and "arranged" should be understood in a broad sense. For example, they may be mechanically connected or electrically connected, or may be It is the internal connection between two elements, which can be directly connected or connected through an intermediate medium. For those skilled in the art, the specific meaning of the above terms can be understood according to the specific circumstances.

First of all, the solid electrolyte junction adjustment material of the present invention mainly includes a polymer substrate that can allow metal ions (such as lithium ions) to move inside the material and a polymer substrate that can dissociate metal salts (such as lithium salts) and act as a plasticizer. Mixed with additives. In addition, the solid electrolyte junction adjustment The whole material is further mixed with an ion supply material and a crystallization inhibitor material. In the following description, metal ions are described as lithium ions, and metal salts are described as lithium salts.

The above-mentioned polymer substrate that can move lithium ions inside the material refers to a material that does not have lithium ions by itself (in the raw material state or in the early stage of the electrochemical reaction), but can transfer lithium ions. For example, it can be selected from Linear structural materials containing salts, such as polyethylene oxide (PEO). Or in addition to being able to move and transmit lithium ions, it is also a material that can increase the mechanical strength of the film due to its own cross-linked form, such as polyethylene glycol diacrylate (PEGDA), polyethylene glycol Poly(ethylene glycol)dimethacrylate(PEGDMA), Poly(ethylene glycol)monomethylether(PEGME)), Poly(ethylene glycol)dimethacrylate(PEGDMA)) glycol)dimethylether(PEGDME)), polyethylene oxide/2,(2-methoxyethoxy)-ethyl glycidyl ether copolymer (poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (PEO/MEEGE)). Or it is a series of Hyperbranched polymers, such as poly[bis(triethylene glycol)benzoate]. Polynitriles series, such as polyacrylonitrile (PAN), poly(methacrylonitrile) (PMAN), poly(N-2-cyanoethyl) ethylamine (poly(N- 2-cyanoethyl)ethyleneamine)(PCEEI)).

The crystallization inhibiting material can be selected from materials that have the effect of reducing crystallinity, such as poly(ethyl methacrylate) (PEMA), poly(methyl methacrylate) (PMMA) ), poly(oxyethylene), poly(cyanoacrylate)(PCA), polyethylene glycol(PEG), poly(vinyl alcohol)(PVA )), polyvinyl butyral (PVB), polyvinyl chloride (Poly(vinyl chloride) (PVC)), polyvinyl chloride-polyethyl methyl acrylate (PVC-PEMA), polyoxyethylene-polymethyl methacrylate (PEO-PMMA), poly(acrylonitrile-co-methyl methacrylate) P(AN-co-MMA) ), polyvinyl alcohol-polyvinylidene fluoride (PVA-PVdF), polyacrylonitrile-polyvinyl alcohol (PAN-PVA), polyvinyl chloride-polyethyl methacrylate (PVC-PEMA). Polycarbonates series, such as poly(ethylene oxide-co-ethylene carbonate) (PEOEC), polyhedral oligomeric silsesquioxane (POSS), Polyethylene carbonate (PEC), poly(propylene carbonate) (PPC)), poly(ethyl glycidyl ether carbonate) (P(Et-GEC) ), poly(t-butyl glycidyl ether carbonate)P(tBu-GEC). Cyclic carbonates series, such as poly(trimethylene carbonate) ) (PTMC)). Polysiloxane-based series, such as polydimethylsiloxane (PDMS), poly(dimethyl siloxane-co-ethylene oxide) P(DMS-co-EO)), Poly(siloxane-g-ethyleneoxide). Polyesters series, such as ethylene adipate, ethylene succinic acid Ester (ethylene succinate), ethylene malonate (ethylene malonate). Furthermore, such as poly (vinylidenedifluoride hexafluoropropylene) (PvdF-HFP), poly (vinylidenedifluoride) ) (PvdF)), Poly(ε-caprolactone) PCL).

The above-mentioned additives that can dissociate the lithium salt and act as a plasticizer can be selected from the plastic crystal electrolytes (PCEs) series, such as succinonitrile (SN) [ETPTA//SN; PEO/SN ；PAN/PVA-CN/SN]), N-ethyl-N-methylpyrrolidine+N,N-diethylpyrrolidine (N-ethyl-N-methylpyrrolidinium,[C2mpyr]+ AnionsN,N-diethyl -pyrrolidinium,[C2epyr]), Quaternary alkylammonium, n-alkyltrimethylphosphonium ([P1,1,1,n]), Decamethylferro-cenium ,[Fe(C ₅ Me ₅ ) ₂ ]), 1-(N,N-dimethylamine)-2-amino-ethyl trifluoromethanesulfonate (1-(N,N-dimethylammonium)-2-( ammonium)ethane triflate([DMEDAH2][Tf]2)), Anions=[FSI],[FSA],[CFSA],[BETA], LiSi(CH ₃ ) ₃ (SO ₄ ), Trimethy (lithium trimethylsilyl sulfate)). Or ionic liquid, which can be selected from the imidazole (IMIDAZOLIUM) series, such as bis(trifluoromethanesulfonyl) imide (ANION/Bis(trifluoromethanesulfonyl) imide), bis(fluorosulfonyl) imide (ANION/ Bis (fluorosulfonyl) imide), trifluoromethanesulfonate (ANION/Trifluoromethanesulfonate). Or ammonium (AMMONIUM) series, such as bis(trifluoromethanesulfonyl) imide (ANION/Bis(trifluoromethanesulfonyl) imide). Or pyridine (PYRROLIDINIUM) series, bis(trifluoromethanesulfonyl) imide (ANION/Bis(trifluoromethanesulfonyl) imide), bis(fluorosulfonyl) imide (ANION/Bis(fluorosulfonyl) imide). Or piperidine (PIPERIDINIUM) series, such as bis(trifluoromethanesulfonyl) imide (ANION/Bis(trifluoromethanesulfonyl) imide), bis(fluorosulfonyl) imide (ANION/Bis(fluorosulfonyl) imide).

The aforementioned ion supply material may be a lithium salt. The lithium salt is, for example, lithium bistrifluoromethylsulfonylimide (LiTFSI), lithium bisfluorosulfonylimide (LiFSI), lithium tetrafluoroborate (LiBF ₄ ), or lithium hexafluorophosphate (LiPF ₆ ).

Furthermore, the solid electrolyte junction adjustment material can be further mixed with a second dopant. The second dopant can be a nano-level passive ceramic material (non-electrolyte oxide) or an inorganic solid electrolyte. Conductive material. When the second dopant is a passive ceramic material, it can reduce the amount of polymer base material and additives used, and improve the film-forming properties. It can be used as a film-forming reinforcing material on the material. For example, silicon dioxide, if it is a nano-level inorganic solid electrolyte, in addition to reducing the amount of polymer substrate and additives used, it can also provide a high-speed ion conduction path. The inorganic solid electrolyte may be, for example, an oxide solid electrolyte or a sulfide solid electrolyte or other inorganic solid electrolyte. For example, when ions are transported in the solid electrolyte interface adjustment material, you can simply select the adjustment material to move, or you can select the nano-level inorganic solid electrolyte as the moving path when it touches the nano-level inorganic solid electrolyte. . If the second dopant is a conductive material, the conductivity can be improved, especially when applied to the polar layer.

In addition, the present invention uses additives to improve the fluidity of the polymer substrate, so that the polymer substrate has higher room temperature ion conductivity and poor mechanical properties, and can be filled between solid electrolyte particles, or solid electrolyte A surface-to-surface (not point-to-point) or approximately wettability contact is achieved between the particle and another heterogeneous particle, thereby reducing the interface resistance of the solid electrolyte. In addition, because additives, such as ionic liquids, will not volatilize, there will be no problem of flammable gas. At the same time, during the dehydration and drying process, the solid electrolyte junction adjustment material will not shrink in size and ions due to the volatilization of internal additives. The continuity drops.

For continuation, please refer to Figure 1a, which is a schematic diagram of an embodiment of a hybrid electrolyte system containing the solid electrolyte junction adjustment material of the present invention. As shown in the figure, the hybrid electrolyte system 1 includes a first particle 11, which is a first inorganic solid electrolyte; a second particle 12, which is selected from a second inorganic solid electrolyte, a passive ceramic material or an active material And a bridging portion 13, which is located between the first particle 11 and the second particle 12, the bridging portion 13 is formed by the solid electrolyte junction adjustment material, and the first particle 11 and the second The particles 12 then form a face-to-face ion transport pathway. As mentioned earlier, the present invention uses additives, such as ionic liquids, to improve the fluidity of the polymer substrate, so that the polymer substrate has higher room temperature ion conductivity. And poor mechanical properties, and can be filled between the first particles 11 and the second particles 12, so that the inorganic solid electrolyte (first particles) can achieve surface-to-surface or nearly wettability contact through the interface adjustment material. A particle (solid electrolyte or active material surface), instead of the traditional solid electrolyte particle, only conducts point-to-point ion transfer through the contact point with another particle. Therefore, the present invention can reduce the interfacial resistance of the solid electrolyte. The foregoing inorganic solid electrolyte may be, for example, an oxide solid electrolyte or a sulfide solid electrolyte or other inorganic solid electrolyte.

，0<θ₁<90。橋接部13與第二顆粒12的接面是弧度r2，該弧度r2對應的圓心角為θ2，弧度r2是2D τ×

，0<θ2<90。因此，第一顆粒11與第二顆粒12是透過接面弧度r1與r2進行離子傳輸，相對的傳統固態電解質顆粒對另一顆粒的點對點接觸方式僅是半徑上的單點，也可以是說θ≒0。 The surface-to-surface or wettability contact system defined by the present invention can be as shown in Figure 1b. If it is assumed that the first particle 11 is spherical and has a radius of D1, the second particle is also spherical and has a radius of D2. , The junction of the bridging portion 13 and the first particle 11 is a radian r1, the central angle corresponding to the radian r1 is θ1, and the radian r1 is 2D τ×

, 0<θ ₁ <90. The junction between the bridging portion 13 and the second particle 12 is a radian r2, the central angle corresponding to the radian r2 is θ2, and the radian r2 is 2D τ×

, 0<θ2<90. Therefore, the first particle 11 and the second particle 12 transmit ions through the arcs of junction r1 and r2. The point-to-point contact of the traditional solid electrolyte particle to another particle is only a single point on the radius, or θ ≒0.

The above-mentioned polymer substrate not only serves as an ion conduction function in this mixed electrolyte system, but also serves as an adhesive and a film-forming agent for adhering the first particles 11 and the second particles 12.

Please refer to Figure 1c, which is a schematic diagram of another embodiment of the present invention. As shown in the figure, the surface of the bridging portion 13 that is not in contact with the first particles 11 and the second particles 12 is further doped/disposed with a plurality of first dopants 14. The first dopants 14 may be the first dopants 14 Three inorganic solid electrolytes with a particle size smaller than the first particles 11 and the second particles 12, or a passive ceramic material (non-electrolyte oxide) that promotes the film-forming effect. Moreover, the first dopant 14 is further extended on the outer surface of the first particle 11 and/or the second particle 12, as shown in FIG. 1d. In addition, when the second particles 12 are active materials, The first dopant 14 may be a conductive substance. The conductive material can be selected from graphite, acetylene black, carbon black, carbon tube, carbon fiber, graphene, or a mixture of any two or more of the above materials.

Please refer to Figure 1e, which is a schematic diagram of another embodiment of the present invention. As shown in the figure, the bridge portion 13 is further mixed with a second dopant 15, which can be a nano-level passive ceramic material or an inorganic solid electrolyte particle. The related descriptions and effects of mixing the second dopant 15 in the solid electrolyte junction adjustment material have been described previously, and will not be repeated here. In addition, when the second particle 12 is an active material, the second dopant 15 may be a conductive material, or a mixture of nano-scale particles (oxide or/solid electrolyte) and a conductive material. The conductive material can be selected from graphite, acetylene black, carbon black, carbon tube, carbon fiber, graphene, or a mixture of any two or more of the above materials.

The embodiment in which the second dopant 15 is mixed in the bridge portion 13 can be combined with the embodiment in FIG. 1c or FIG. 1d. For example, as shown in FIG. 1f, the bridge portion 13 is mixed with a second dopant. In addition to the dopants 15, the surface of the bridging portion 13 that is not in contact with the first particles 11 and the second particles 12 is further doped/disposed with several first dopants 14.

In the subsequent embodiments, the elements with the same structure, material or characteristic conditions will be described with the same names and element symbols previously.

Please refer to FIG. 2a, which is a schematic diagram of another embodiment of the hybrid electrolyte system containing the solid electrolyte junction adjustment material of the present invention. As shown in the figure, the hybrid electrolyte system 2 includes a first particle 11, which is a first inorganic solid electrolyte; a second particle 12, which is selected from a second inorganic solid electrolyte, a passive ceramic material or an active material; And a first shell layer 21 covering the outer surface of the first particles 11; wherein the first shell layer 21 is formed by the above-mentioned solid electrolyte junction adjustment material, and the solid electrolyte junction adjustment material will The first particle and the second particle then form a non-single-point ion transport path. Based on solid electrolyte junction adjustment material is Materials with poor mechanical strength characteristics, so the second particles 12 and the first shell layer 21 composed of solid electrolyte interface adjustment materials will be in an approximate wet surface contact mode, rather than point-to-point, as shown in Figure 2a Partially enlarged as shown in Figure 2a'. Subsequent components constructed using solid electrolyte junction adjustment materials will come into contact with such a wetted surface when they touch hard or fixed-appearance materials (particles).

Please refer to FIG. 2b. The difference compared with the embodiment in FIG. 2a is that the outer surface of the first shell layer 21 is more doped/disposed with a plurality of first dopants 14. Please refer to FIG. 2c. The difference from the embodiment in FIG. 2b is that the first shell layer 21 is mixed with the second dopant 15. Referring to FIG. 2d, a second shell layer 22 may also be formed on the outer surface of the second particle 12, and the second shell layer 22 is also formed of the aforementioned solid electrolyte junction adjustment material.

Please refer to FIG. 2e. The difference from the embodiment in FIG. 2d is that the outer surface of the first shell layer 21 and/or the second shell layer 22 is more doped/disposed with a plurality of first dopants 14. Please refer to FIG. 2f. The difference from the embodiment in FIG. 2e is that the first shell layer 21 and/or the second shell layer 22 is mixed with the second dopant 15.

Please refer to FIG. 3a, which is a schematic diagram of another embodiment of the hybrid electrolyte system containing the solid electrolyte junction adjustment material of the present invention. As shown in the figure, the hybrid electrolyte system 3 includes a first particle 11, which is a first inorganic solid electrolyte; a second particle 12, which is a second inorganic solid electrolyte or active material; and a first shell layer 21, It covers the outer surface of the first particle 11; a second shell layer 22 which covers the outer surface of the second particle 12; and a bridge 13 which is located between the first shell layer 21 and the second shell layer 21 Between the shell layers 22 and connected or connected to the first shell layer 21 and the second shell layer 22; wherein the first shell layer 21, the second shell layer 22 and the bridge portion 13 are all made of the solid state The electrolyte junction adjustment material is formed, and the solid electrolyte junction adjustment material It becomes the surface-to-surface ion transfer path of the first particle and the second particle.

Please refer to FIG. 3b. The difference compared with the embodiment in FIG. 3a is that the surface of the bridge 13 that is not in contact with the first shell layer 21 and the second shell layer 22 is more doped/disposed with several A dopant 14. Please refer to FIG. 3c, which is different from the embodiment in FIG. 3b in that the first dopant 14 is further extended on the outer surface of the first shell layer 21 and/or the second shell layer 22.

Please refer to Fig. 3d, which is different from the embodiment in Fig. 3c in that the solid electrolyte junction adjustment material that composes the first shell layer 21, the second shell layer 22, and the bridge portion 13 is mixed with a second dopant. Sundries 15.

Please refer to FIG. 3e, which is different from the embodiment in FIG. 3d in that the first dopant 14 is further extended on the outer surface of the first shell layer 21 and/or the second shell layer 22.

In the above embodiments, when the second particle 12 is an active material, the hybrid electrolyte system can be applied to the electrode layer, and an artificial passive film can be formed on the surface of the second particle 12 to avoid electrolyte (solid electrolyte). The structural degradation of the active material caused by the junction adjustment material, and the resulting decrease in surface conductivity and the rate of lithium ions passing through the surface layer. For example, as shown in FIG. 1g, an artificial passive film 16 may be formed on the surface of the second particles 12. Or, as shown in FIG. 2g, FIG. 2h, and FIG. 3f, an artificial passivation film 16 may be formed on the surface of the second particles 12. The artificial passive film 16 is sandwiched between the second particles 12 and the second shell layer 22. The main purpose of the artificial passive film 16 is to reduce or avoid excessive contact between the components of the solid electrolyte junction adjustment material and the second particles 12. The artificial passive film 16 can be divided into a non-solid electrolyte series and a solid electrolyte series according to the ion transportability. The thickness of the artificial passive film 16 is roughly less than 100 nm. The non-solid electrolyte series can be conductive materials, ceramic materials without lithium ions, or a mixture of these two materials. The lithium-free ceramic material can be selected from zirconia, silicon oxide, aluminum oxide, titanium oxide, or gallium oxide.

When the second particles 11 are selected from inorganic solid electrolytes or passive ceramic materials, the hybrid electrolyte system can be applied to the isolation layer, and the hybrid electrolyte system needs to have ion supply materials, such as salts. Furthermore, when the first particles 11 and the second particles 12 are both inorganic solid electrolytes and do not have a shell structure, the materials of the first particles 11 and the second particles 12 must be selected according to the position of the battery element. For example, when the hybrid electrolyte system is applied to the positive electrode side, the first particles 11 and the second particles 12 can be lithium aluminum titanium phosphate (LATP) or lithium blue zirconium oxide (LLZO), and when the hybrid electrolyte The system is applied to the negative electrode side, and the first particles 11 and the second particles 12 can be selected from LLZO to avoid reduction reaction when LATP containing titanium is used in the negative electrode. However, when the outer surfaces of the first particles 11 and the second particles 12 are provided with a shell layer, there is no need to adjust the type of solid electrolyte used according to the type of the electrode layer (positive or negative electrode), that is to say, the first particle 11 and the second particle 12 can be LATP with lower cost and applied to positive and negative poles.

In summary, the first dopant 14 of the present invention can be selected from three types, the first type is a solid electrolyte, and the particle size is smaller than the first particles 11 and the second particles 12; the second type The type is a passive ceramic material, which can not only reduce the amount of solid electrolyte junction adjustment material, but also can be used as a film-forming reinforcement; the third type is a conductive material, which is mainly used in the electrode layer. The first type and the second type are applicable to both polar layers and interlayers.

The particle size or size of the second dopant 15 of the present invention is nanometer level, and can also be selected from three types, the first type is solid electrolyte; the second type is passivation Ceramic material, in addition to reducing the amount of solid electrolyte junction adjustment material, can be used as a film-forming reinforcement; the third type is a conductive material, which is mainly used in the electrode layer. The first type and the second type are applicable to both polar layers and interlayers.

For example, when the second particles 12 are active materials, the solid electrolyte adjustment material (does The second dopant (nano-level particles) 15 mixed or filled for the bridge portion and/or shell layer may be a solid electrolyte, a passive ceramic material, or a conductive material, or any two or more of the above materials the mix of. Similarly, if the second particle 12 is an active material, the surface of the first particle 11, the second particle 12, or any surface of the first shell layer 21, the second shell layer 22, and the bridging portion 13 may be provided with a first dopant. Impurities 14, the first dopant 14 may be a solid electrolyte, a passive ceramic material, or a conductive material, or a mixture of any two or more of the foregoing materials.

Please refer to Figure 4, which is a graph of the ion conduction characteristics of the solid electrolyte junction adjustment material of the present invention and the solid electrolyte LATP at low and high frequencies. In this figure, curve A represents LATP, and curve B represents the present invention. The solid electrolyte junction adjustment material without ion supply material, curve C represents the hybrid electrolyte system containing the solid electrolyte junction adjustment material of the present invention (which can be regarded as a mixture of 70% A and 30% B by weight), It does not contain ion supply materials, and LATP is equivalent to the first particle in the specification. Curve D is the component of curve C with lithium ions added. It can be seen from the figure that in the high frequency region, the solid oxide electrolyte LATP has better ion conductivity. Therefore, it can be seen that in the high frequency state, the movement of ions tends to be mainly in the homogeneous structure of the solid oxide. Homogeneous structure generally refers to the homogeneous structure of either vitreous or solid solution in the crystal. On the other hand, in the middle and low frequency region, the solid electrolyte junction adjustment material of the present invention without ion supply material performs better, so it can be seen that In the low-frequency region, the movement mode of ions is mainly the solid/solid interface (heterophase). The solid electrolyte junction adjustment material of the present invention has a better surface because it produces a better surface-to-surface contact mode (approximately liquid wetted contact). Therefore, the hybrid electrolyte of the present invention adopts the components of curve A and curve B to be mixed in a specific ratio. It can be seen from the figure that the ion conductivity characteristics (curve C or D) can be maximized through this mixing method. Good low frequency and high frequency are superior.

In addition, from the curve C in Figure 4, it can be found that when the volume percentage of _{the junction adjusting material is A 0} and the volume percentage is B ₀ (A ₀ +B ₀ ≒100, A ₀ is 30-40, and B ₀ is 70 -60) solid electrolyte mixed to obtain a hybrid solid electrolyte system (when the second dopant 15 is a solid electrolyte, it is also included in the percentage B), if the junction adjustment material is used to contact the active electrode layer When the material is used, the ratio of the solid electrolyte adjusting material to the solid electrolyte in the hybrid electrolyte system can be appropriately adjusted as the junction adjusting material is A ₁ , and the amount of solid electrolyte is B ₁ , A ₁ +B ₁ =100, 50<A ₁ <100. Conversely, if the hybrid electrolyte system is far away from the active material, the volume of the solid electrolyte adjustment material for the entire hybrid electrolyte system is A ₂ , and the solid electrolyte is B ₂ , A ₂ +B ₂ =100, 50<B _{2 <100} As a result, it will be able to more effectively meet the low-frequency conduction requirements close to the active material, and the high-frequency conduction demand is located far away from the active material, so a higher solid electrolyte content is used. That is to say, with the distance from the outer surface of the active material from close to far, the junction adjustment material in the hybrid solid electrolyte system exhibits a high to low drop volume ratio content distribution. In other words, a battery composed of this hybrid electrolyte system includes an active material layer and an isolation layer. When the hybrid electrolyte system is applied to the isolation layer, the volume content of the solid electrolyte junction adjustment material It is smaller than the volume content of the solid electrolyte in the hybrid electrolyte system. When the hybrid electrolyte system is applied to the active material layer, the closer to the surface of the active material, the higher the volume content of the solid electrolyte junction adjustment material compared to the volume content of the solid electrolyte in the hybrid electrolyte system.

In summary, the present invention proposes a new solid electrolyte junction adjustment material and its hybrid electrolyte system applied to electrochemical systems (such as lithium ion secondary batteries). This solid electrolyte adjustment material mainly uses a polymer base material that can move metal ions inside the material and a dissociable metal salt and is mixed as a plasticizer additive, so that the oxide solid electrolyte particles are mixed with another The contact surface of the granular material forms a relatively liquid wet contact or surface The contact type to the surface, thereby effectively reducing the problem of high interface impedance of the oxide solid electrolyte.

Only the above are only preferred embodiments of the present invention and are not used to limit the scope of implementation of the present invention. Therefore, all equivalent changes or modifications made in accordance with the characteristics and spirit of the application scope of the present invention should be included in the patent application scope of the present invention.

1‧‧‧Hybrid electrolyte system

11‧‧‧First particle

12‧‧‧Second particle

13‧‧‧Bridge

Claims (49)

A solid electrolyte junction adjustment material, which is used in an electrochemical system and is located on the surface of a solid electrolyte. The solid electrolyte junction adjustment material is mainly composed of a polymer substrate that allows metal ions to move inside the material and a It is a mixture of dissociable metal salts and used as plasticizer additives. The solid electrolyte junction adjustment material described in claim 1 further includes a crystallization suppressing material. The solid electrolyte junction adjustment material described in claim 1 is further mixed with an ion supply material. The solid electrolyte junction adjustment material according to claim 3, wherein the ion supply material is a lithium salt. The solid electrolyte junction adjustment material according to claim 1, wherein the solid electrolyte junction adjustment material is further mixed with a second dopant whose size is on the nanometer level, and the second dopant is selected from inorganic solid Electrolyte, passive ceramic material, conductive material, or a mixture of two or more of the above materials. The solid electrolyte junction adjustment material according to claim 1, wherein the polymer substrate is selected from polyethylene oxide (PEO), polyethylene glycol diacrylate (PEGDA), Poly(ethylene glycol)dimethacrylate(PEGDMA), Poly(ethylene glycol)monomethylether(PEGME)), Poly(ethylene glycol)dimethacrylate(PEGDMA)), Poly(ethylene glycol)monomethylether(PEGME)) (ethylene glycol)dimethylether(PEGDME)), polyethylene oxide/2,(2-methoxyethoxy)-ethyl glycidyl ether co Polymer (poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether](PEO/MEEGE)), Hyperbranched polymers series or Polynitriles series. The solid electrolyte junction adjustment material according to claim 1, wherein the additive material is plastic crystal electrolytes (PCEs) or ionic liquids. A hybrid electrolyte system, which contains: A first particle, which is a first inorganic solid electrolyte; A second particle selected from a second inorganic solid electrolyte, a passive ceramic material or an active material; and A bridging portion is located between the first particle and the second particle, the bridging portion is formed by a solid electrolyte junction adjustment material, and the first particle and the second particle then form an ion transfer path , Wherein the solid electrolyte junction adjustment material is mixed with a polymer base material that can allow lithium ions to move inside the material, and a dissociable lithium salt and an additive material as a plasticizer. The hybrid electrolyte system according to claim 8, wherein the solid electrolyte junction adjustment material further includes a crystallization suppressing material. The hybrid electrolyte system according to claim 8, wherein the solid electrolyte junction adjustment material is further mixed with an ion supply material. The hybrid electrolyte system according to claim 10, wherein the ion supply material is a lithium salt. The hybrid electrolyte system according to claim 8, wherein when the second particles are selected from a second inorganic solid electrolyte or a passive ceramic material, the solid electrolyte junction adjustment material is further mixed with a second dopant, Its size is nanometer level, and the second dopant is selected from inorganic solid electrolytes, passive ceramic materials or their mixtures. The hybrid electrolyte system according to claim 8 or 12, wherein when the second particle is selected from a second inorganic solid electrolyte or a passive ceramic material, the bridging portion is not connected to the first particle and the second particle The contacting surface is further doped/disposed with several first dopants, and the first dopants are selected from inorganic solid electrolytes, passive ceramic materials or their mixtures. The hybrid electrolyte system according to claim 8, wherein when the second particle is an active material, the solid electrolyte junction adjustment material is further mixed with a second dopant whose size is on the nanometer level, and the second dopant The impurities are selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more thereof. The hybrid electrolyte system according to claim 8 or 14, wherein when the second particle is an active material, the bridging portion is more doped/disposed on a surface not in contact with the first particle and the second particle The first dopant, the first dopant is selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more. The hybrid electrolyte system according to claim 13 or 15, wherein the first dopant is further extended on the outer surface of the first particle and/or the second particle. The hybrid electrolyte system according to claim 8, wherein when the second particle When the particles are active materials, the surface of the second particles has an artificial passive film. The hybrid electrolyte system according to claim 8, wherein the polymer substrate is selected from polyethylene oxide (PEO), polyethylene glycol diacrylate (PEGDA), polyethylene glycol Poly(ethylene glycol)dimethacrylate(PEGDMA), Poly(ethylene glycol)monomethylether(PEGME)), Poly(ethylene glycol)dimethacrylate(PEGDMA)) glycol)dimethylether(PEGDME)), polyethylene oxide/2,(2-methoxyethoxy)-ethyl glycidyl ether copolymer (poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (PEO/MEEGE)), Hyperbranched polymers series or Polynitriles series. The hybrid electrolyte system according to claim 8, wherein the additive is plastic crystal electrolytes (PCEs) or ionic liquids. A hybrid solid electrolyte system, which includes: A first particle, which is a first inorganic solid electrolyte; A second particle selected from a second inorganic solid electrolyte, a passive ceramic material or an active material; and A first shell layer covering the outer surface of the first particle; Wherein the first shell layer is formed by a solid electrolyte junction adjustment material, and the first particles and the second particles then form an ion transfer path, wherein the solid electrolyte junction adjustment material is made of a metal ion The polymer base material that moves inside the material is mixed with a dissociable metal salt and used as an additive of plasticizer. The hybrid electrolyte system according to claim 20, wherein the solid electrolyte junction adjustment material further includes a crystallization suppressing material. The hybrid electrolyte system according to claim 20, wherein the solid electrolyte junction adjustment material is further mixed with an ion supply material. The hybrid electrolyte system according to claim 22, wherein the ion supply material is a lithium salt. The hybrid electrolyte system according to claim 20, wherein when the second particles are selected from a second inorganic solid electrolyte or a passive ceramic material, the solid electrolyte junction adjustment material is further mixed with a second dopant, Its size is nanometer level, and the second dopant is selected from inorganic solid electrolytes, passive ceramic materials or their mixtures. The hybrid electrolyte system according to claim 20 or 24, wherein when the second particles are selected from a second inorganic solid electrolyte or a passive ceramic material, the outer surface of the first shell layer is more doped/disposed There are several first dopants, and the first dopants are selected from inorganic solid electrolytes, passive ceramic materials or mixtures thereof. The hybrid electrolyte system according to claim 20, wherein when the second particle is an active material, the solid-state electrolyte junction adjustment material is further mixed with a second dopant whose size is on the order of nanometers, and the second dopant The impurities are selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more thereof. The hybrid electrolyte system according to claim 20, wherein when the second When the particles are active materials, the surface of the first shell layer is further doped/disposed with several first dopants, and the first dopants are selected from inorganic solid electrolytes, passive ceramic materials, conductive materials or any Mix the two or more. The hybrid electrolyte system according to claim 20, wherein when the second particle is an active material, the surface of the second particle has an artificial passive film. The hybrid solid electrolyte system according to claim 20, wherein a second shell layer is formed on the outer surface of the second shell particle, and the second shell layer is formed by the solid electrolyte junction adjustment material. The hybrid electrolyte system according to claim 29, wherein when the second particles are selected from a second inorganic solid electrolyte or a passive ceramic material, the solid electrolyte junction adjustment material is further mixed with a second dopant, Its size is nanometer level, and the second dopant is selected from inorganic solid electrolytes, passive ceramic materials or their mixtures. The hybrid electrolyte system according to claim 29 or 30, wherein when the second particle is selected from a second inorganic solid electrolyte or a passive ceramic material, the first shell layer and/or the second shell The outer surface of the layer is further doped/disposed with a number of first dopants, and the first dopants are selected from inorganic solid electrolytes, passive ceramic materials, or mixtures thereof. The hybrid electrolyte system according to claim 29, wherein when the second particle is an active material, the solid electrolyte junction adjustment material is further mixed with a second dopant whose size is on the nanometer level, and the second dopant The impurities are selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more thereof. The hybrid electrolyte system according to claim 29 or 32, wherein when the second particle is an active material, the surface of the first shell layer and/or the second shell layer is more doped/disposed with a plurality of first The dopant, the first dopant is selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more. The hybrid solid electrolyte system according to claim 29, wherein when the second particle is an active material, the surface of the second particle has an artificial passive film, and the artificial passive film is located between the second particle and the first particle. Between the two shells. The hybrid solid electrolyte system according to claim 20, wherein the polymer substrate is selected from polyethylene oxide (PEO), polyethylene glycol diacrylate (PEGDA), and poly(ethylene glycol) diacrylate (PEGDA). Poly(ethylene glycol)dimethacrylate(PEGDMA), Poly(ethylene glycol)monomethylether(PEGME)), Poly(ethylene glycol)dimethacrylate(PEGDMA), Poly(ethylene glycol)monomethylether(PEGME)) ethylene glycol)dimethylether(PEGDME)), poly(ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether copolymer), poly(ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether)/2,(2-methoxyethoxy)-ethyl glycidyl ether copolymer ] (PEO/MEEGE)), Hyperbranched polymers series or Polynitriles series. The hybrid electrolyte system according to claim 20, wherein the additive is plastic crystal electrolytes (PCEs) or ionic liquids. A hybrid solid electrolyte system, which includes: A first particle, which is a first inorganic solid electrolyte; A second particle, which is selected from a second inorganic solid electrolyte, a passive ceramic material or an active material; A first shell layer covering the outer surface of the first particle; A second shell layer covering the outer surface of the second particle; and A bridge portion located between the first shell layer and the second shell layer, and then the first shell layer and the second shell layer; Wherein the first shell layer, the second shell layer and the bridge portion are all formed by a solid electrolyte junction adjustment material, and the first particles and the second particles then form an ion transport path, and the solid electrolyte is connected The surface conditioning material is mixed with a polymer base material that can move metal ions inside the material and a dissociable metal salt as an additive material for plasticizers. The hybrid electrolyte system according to claim 37, wherein the solid electrolyte junction adjustment material further includes a crystallization suppressing material. The hybrid electrolyte system according to claim 37, wherein the solid electrolyte junction adjustment material is further mixed with an ion supply material. The hybrid electrolyte system according to claim 39, wherein the ion supply material is a lithium salt. The hybrid electrolyte system according to claim 37, wherein when the second particles are selected from a second inorganic solid electrolyte or a passive ceramic material, the solid electrolyte junction adjustment material is further mixed with a second dopant, Its size is nanometer level, and the second dopant is selected from inorganic solid electrolytes and passive ceramic materials Or a mixture of them. The hybrid electrolyte system according to claim 37 or 41, wherein when the second particle is selected from a second inorganic solid electrolyte or a passive ceramic material, the first shell, the bridge or the second shell The outer surface of the layer is further doped/disposed with a number of first dopants, and the first dopants are selected from inorganic solid electrolytes, passive ceramic materials, or mixtures thereof. The hybrid electrolyte system according to claim 37, wherein when the second particle is an active material, the solid-state electrolyte junction adjustment material is further mixed with a second dopant whose size is on the order of nanometers, and the second dopant The impurities are selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more thereof. The hybrid electrolyte system according to claim 37 or 43, wherein when the second particle is an active material, the surface of the first shell layer, the bridge portion or the second shell layer is more doped/disposed with several A dopant, the first dopant is selected from inorganic solid electrolytes, passive ceramic materials, conductive materials, or a mixture of any two or more. The hybrid electrolyte system according to claim 37, wherein when the second particle is an active material, the surface of the second particle has an artificial passive film, and the artificial passive film is located between the second particle and the second particle. Between shells. The hybrid solid electrolyte system according to claim 37, wherein the polymer substrate is selected from polyethylene oxide (PEO), polyethylene glycol diacrylate (PEGDA), and poly(ethylene glycol) diacrylate (PEGDA). Poly(ethylene glycol) dimethacrylate (PEGDMA), polyethylene glycol Poly(ethylene glycol)monomethylether(PEGME)), Poly(ethylene glycol)dimethylether(PEGDME)), polyethylene oxide/2,(2-methoxyethoxy )-Ethyl glycidyl ether copolymer (poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether](PEO/MEEGE)), Hyperbranched polymers series or Polynitriles )series. The hybrid electrolyte system according to claim 37, wherein the additive is plastic crystal electrolytes (PCEs) or ionic liquids. A battery composed of the hybrid electrolyte system described in claim 8 or 20 or 37, the battery comprising an active material layer and an isolation layer, when the hybrid electrolyte system is applied to the active material layer, the hybrid electrolyte system The closer the electrolyte system is to the surface of the active material in the active material layer, the higher the volume ratio of the junction adjusting material in the hybrid solid electrolyte system. A battery composed of the hybrid electrolyte system described in claim 8 or 20 or 37. The battery includes an active material layer and an isolation layer. When the hybrid electrolyte system is applied to the isolation layer, the solid electrolyte is connected to The volume content of the surface adjusting material is less than the volume content of the inorganic solid electrolyte in the hybrid electrolyte system.

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